The song was released as the album's fifth single in late 2005 along with a remix. A music video featuring rapper Slim Thug was also released which featured the Harajuku Girls as well. The track received mixed reviews from critics, who generally found the track less impressive than the previous singles. It entered the top forty worldwide but had mediocre success overall and was less popular than the previous singles from L.A.M.B.

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Stefani had an emotional breakdown from difficulties collaborating with many other artists and songwriters, so No Doubt bassist Tony Kanal invited her to his house.[1] Kanal had been working on a track, which later became "Crash", the sixth single from the album.[2] However, the two were unable to write anything following that, because they had differing ideas of how the music should sound.[1] Stefani commented that "it was just frustrating and embarrassing to sit there and think we could write songs."[2] Six months later, the two returned to work and came up with the beginnings of a song while working in Kanal's bedroom.[2][3] The two experimented with combining various melodies and including what Stefani referred to as "this really kinda fast rappy part".[3] This was the last song she and Kanal wrote together for the album.[4]

"Luxurious" is a slow jam love song with instrumentation from keyboards and synthesizers.[5] It is written in common time in the key of A minor. The song uses a descending i-vii-VI-V chord progression.[6] The lyrics of the song include descriptions of wealth and riches, what one reviewer called "a world of Egyptian cotton, cashmere, tuberoses, and, of course, diamonds".[7] Stefani stated that "[the] song really is more about a love relationship. If you really listen to the lyrics, it has nothing to do with money or luxury. It has to do with love, being rich in love. I just wanted to think of a clever way to express how you have to work really hard for the rewards of that."[3] The single version of the song contains an additional verse from rapper Slim Thug for release to urban radio and clubs.[8]

The song begins with Stefani's husband Gavin Rossdale speaking in French[5] and then leads into the first verse. The lyrics describe Stefani talking about "flying first class" and "livin' like a queen". She talks about being luxuriously in love and calls her lover Limousine and Treasure Chest. She talks about the increasing passion between her and her partner, and says, "Our passion it just multiplies" and "got in the fifth gear, baby". In the chorus she tells that love is getting expensive and she and her partner have to work hard night and day to be rich in love, and after working hard, when they lay back together, they get the payback. After the second verse, the song gets slower and Stefani repeats "Cha-ching, cha-ching" four times alternated with lines talking about getting "hooked up with the love" and "hydroponic love". The song ends with Gavin Rossdale speaking more lines in French.[5]

The song received mixed reviews from music critics. Bill Lamb of About.com commented that "[i]f Madonna is wishing to pass on her 'Material Girl' title, Gwen Stefani is happy to wear it proudly", but noted that "[t]hings are wearing a little thin, and this song doesn't have the striking impact of 'Rich Girl' or 'Hollaback Girl'."[7] Sam Shepherd of musicOMH agreed, saying that "'Luxurious' is by no means a bad song, but it is pretty ordinary when compared to the songs that have preceded it."[9]PopMatters' Jason Damas found the track uninteresting and said that Rossdale's appearance "sounds like a blinged-out Saint Etienne".[10] Alex Lai from Contactmusic.com called Stefani's performance "as seductive as ever, and the production extremely polished, but it lacks the infectiousness of her other releases"; he found Slim Thug's remix unnecessary and called the single's release "a money-spinning exercise".[11] Laura Heaps from MyVillage agreed, stating that the single "just doesn't stand out" and that Stefani "doesn't do hip hop as well as she does quirky pop",[8] and Playlouder's Richard Smirke called the track a "sickly sweet R&B ballad".[12] Sal Cinquemani of Slant Magazine called the lyrics "surprisingly sharp";[13] Nick Sylvester of Pitchfork Media disagreed, referring to the song as a "soulless Nellee Hooper 90s R&B vanity affair" and a "zombied buy-LAMB-clothing mantra".[14]

"Luxurious" had decent success in North America. In the United States, the single debuted on the Billboard Hot 100 at number eighty on the issue dated November 5, 2005.[15] It failed to reach the top twenty, peaking at number twenty-one five weeks later, and remained on the chart for twenty weeks.[16] It performed better on the pop-oriented charts, reaching number ten on the Top 40 Mainstream, number thirteen on the Pop 100, and number thirty-seven on the Adult Top 40.[17] The track also had some crossover success, charting at number nine on the Rhythmic Top 40 and number thirty-three on the Hot R&B/Hip-Hop Songs.[17] In Canada, the single was released to radio on October 25, 2005. It reached number twenty-one on the Canadian BDS Airplay Chart, and remained in the top one-hundred for twelve weeks.[18] "Luxurious" was more successful on the Canadian Singles Chart, where it peaked at number ten in its sixth week on the chart.[18]

The song was released on December 5, 2005 in Europe and Australia. It received very little promotion in the UK and continued the trend of Stefani's lower-charting singles since "Hollaback Girl" when it debuted at number forty-four and dropped off the UK Singles Chart after only one more week.[19] The single performed similarly throughout Europe, where it reached the top forty in Ireland, Italy, the Netherlands, and Switzerland, but generally did not reach the top thirty.[20] It did particularly well in Finland, where it charted at number two, thus becoming the highest-peaking single of Stefani's solo career in that country, although it spent only two weeks on the chart.[21] Stefani's previous four singles had been successful in Australia, where all reached the top ten; however, "Luxurious" did not reach the top twenty and reached a peak of number twenty-five.[22] In New Zealand, "Luxurious" was moderately successful, where it reached number seventeen but stayed on the chart for only ten weeks.[23]

The music video for "Luxurious" was directed by Sophie Muller. In the video, Stefani plays a chola in high school.[3] Then Stefani, accompanied by her Harajuku Girls, receive a manicure at a beauty salon, and styling her hair and applying cosmetics in front of a mirror. She shows off gold jewellery with her name carved on it. During his rap, Slim Thug appears in sequences with either Stefani or two Harajuku Girls. It concludes with Stefani joining her friends in a block party, where they celebrate with breakdancing and a barbecue. The video is intercut with sequences of Stefani breaking open piñatas and lying on a candy-covered floor, styled in a fashion resembling Mexican painter Frida Kahlo.[24][25]

Stefani had generally developed music video concepts while writing the song, but since she had not expected "Luxurious" to become a single, she had not given much thought to a music video for the song. The image she had for her persona was a high school girl named Mercedes, who she described as "very inspiring":[3]

She's this total like chola girl, white face, and she used to sit in class and put on tons of makeup. And I used to just watch her, mesmerized. And she would just wear this dark liner and this red lipstick and she had this safety pin and she'd be picking her eyelashes apart. She hadn't taken that mascara off for months.[3]

Stefani called Muller, who had directed several videos for Stefani and No Doubt, to direct the music video. Muller did not understand Stefani's vision for the video, so Stefani became involved in developing ideas for the video.[3]

The video had mediocre success on music video programs. On MTV's Total Request Live, the video debuted on October 25, 2005 at number ten.[26] It peaked at number seven and left the countdown after only five days.[27] After its October 21 debut on MuchMusic's Countdown, it peaked at number eleven nine weeks later, remaining on the chart for thirteen weeks.[28] The video was featured on an episode of MuchMusic's Video on Trial, where the reviewers found it a superficial attempt to market to various races.[29]